N-alkyl-n-sec. butylbenzamides

ABSTRACT

Described are compounds of the formula:   WHEREIN: X Cl, Br, I, CH3; Y H, Cl, Br, I, F, CH3; n 1 or 2, Z alkyl having from 1 to 5 carbon atoms, for n 2, X and Y NOT = CH3. These compounds are useful as selective herbicides.

United States Patent [191 Arsura et al.

451 Sept. 10, 1974 N-ALKYL-N-SEC. BUTYLBENZAMIDES Inventors: Emilio Arsura, S. Donato Milanese;

Agostino Baruffini; Franco Gialdi,

both of Pavia; Giovanni Pellegrini,-

Milan; Riccardo Ponci, Pavia; Pietro Scrivani, Milan, all of Italy Assignee: Montedison S.p.A., Milan, Italy Filed: Nov. 8, 1968 Appl. No.: 774,475

Foreign Application Priority Data Nov. 9, 1967 Italy 22494A/67 Oct. 8, I968 Italy 22207A/68 US. Cl. 260/558 D, 260/558 R, 71/118 Int. Cl. C07c 103/22 Field of Search 260/558 References Cited UNITED STATES PATENTS 9/1967 Dorfman et al 260/558 OTHER PUBLICATIONS Fearn et al., .I. Agr. & Food Chemistry, Vol. 13, p. 116-117. (I965).

Primary Examiner-Harry I. Moatz Attorney, Agent, or Firm-Herbert L. Lerner [57] ABSTRACT Described are compounds of the formula:

sec.C H

10 Claims, 1 Drawing Figure o s s assass 0051 none' mono:

con 0oz: ooslnonm one N-ALKYL-N-SEC. BUTYLBENZAMIDES Our invention relates to new products having a herbicidal action, the compositions which contain them and their use as herbicides.

For quite a number of years now, research work has been steadily going on throughout the world in the field of herbicides, in an effort to find products possessing great effectiveness combined with great specificity. For practical purposes, the specificity of action is of extreme importance because it makes possible the selective disherbing of the infesting plants while leaving the useful plants unharmed.

A number of useful substances have been found for this purpose. However, the necessity for agents having a particular balance of properties and which display specific properties, is still strongly felt. Furthermore, other characteristics are necessary to qualify a satisfactory herbicide. Such characteristics are for instance toxicity for warm-blooded animals, persistence of action, degradability in the soil, etc. Thus it is easily understandable how research in this field will always remain open so that for specific applications further technical progress may ensue.

This invention contributes to the technical progress in this field by teaching, in the'class of halo(alkyl)-N,N- dialkylbenzamides, a particular group of compounds endowed with a marked specific action associated to a remarkable efficacy and to other favorable characteristics. This group of new substances, which constitute an object of this invention, is represented by the formula:

S80.CHo

o o N X i l wherein X Cl, Br, I, CH

Y H, Cl, Br, I, F, CH

n 1 or 2,

Z alkyl with one to five carbon atoms, and for n 2, X and Y both are not CH A further object of this invention are compositions which contain one or more substances of the above formula, in conjunction with means currently in use in the formulation technique, in order to obtain a regular and uniform distribution of relatively small quantities of the herbicidal active ingredients on wide expanses of soil or on the vegetation. The compositions may optionally contain other active ingredients that may develop a complementary action.

In a broad sense, the use of these compounds, no matter what composition contains them nor the technique applied in the treatments, is also within the scope of this invention.

It is well known that the literature shows a herbicidal action of compounds belonging to the class of benzamides (J. Sci. Food Agric. Nov. 10, 1959, pages 577-584 Pizey and L. Wain).

Furthermore, French Pat. No. 1,446,959, published on January 20, 1967, discloses a class of compounds of the formula:

wherein R is alkyl with two or three carbon atoms; R is hydrogen or alkyl as defined above, and where n is a whole number with values from 1 to 3 included. US.

Pat. No. 3,231,360 claims the use of 3- and 4-bromo- N,N-dialkenyl-benzamides.

The compounds according to the instant invention remarkably differ from those of the above-cited patents and from others of similar classes mentioned in the literature, because of a greater effectiveness or for a greater and different specificity of action which clearly reveals itself in the results obtainable in the selective disherbing of weeds as well as in the external manifestation of suffering by the plants treated. Thus, of course, one must assume that there is a different mechanism of action.

The observation of such results has definitely been unexpected and surprising since the herbicidal effectiveness in the halo(alkyl)-N,N-dialkyl-benzamides is decreased when the number of carbon atoms of the alkyl groups is 3, so that, for instance, the halo(alkyl- )-N,N-di-n.butyl-benzamides and the halo(alkyl)-N,N- di-n.amyl-benzamides are almost inactive. On the other hand, a notable difference of activity between the halo-N,N-dialkyl-benzamides with alkyls having a number of carbon atoms less than 4 with a linear chain, and the corresponding compounds with a branched chain, is not observed.

Thus it was absolutely unforeseeable that a substantial shift in the values of the herbicidal activity would occur in the halo-N,N-di-secbutyl-benzamides in comparison to the corresponding halo-N,N-di-n.butylbenzamides.

The N-sec.butyl-N-alkyl-benzamides of formula (I) can be easily prepared by using the known processes for the preparation of the benzamides. They can be prepared for instance by reacting the chlorides of the halo(alkyl)benzoic acids of the formula:

(wherein X, Y and n have the above-described meaning) with di-sec.-butylamine or with sec.-butylalkylamine.

The halobenzoic acids forming intermediates for the preparation of the compounds according to this invention are known and their preparation is found easily in the literature.

We cite, for instance:

Rec. Trav. Chim. 51, 98-113 (1932),

Rec. Trav. Chim. 50, 753-92 (1931),

Rec. Trav. Chim. 49, 1082-92 (1930);

Acta Acad. Aboensis Math.Phys. 8, (4), (1934);

Monatsh 62, 344-8 (1954);

Russian Patent 44,548

J. Indian Chem. Soc. 19, 487-8 (1942);

J. Indian Chem. Soc. 1955, 4139-40;

Med. Proc. SSSR 10, (4), 11-14 (1956);

French Patent No. 835,727

J. Chem. Soc. 1951, 1211;

Rec. Trav..Chim. 21, (1902), 383;

.1. Chem. Soc. 1901, 4349;

J. Chem. Soc. 1903, 332.

Di-sec.butylamine is known; however, some of the sec.butyl-alky1amines, which are used for preparing some of the compounds according to the invention, are new. Anyhow, also the latter are easily obtained by operating according to Campbell et a1. J. Am. Chem. Soc. 66, 82-84, 1944; to British Patents Nos. 600,841 and 602,332; .1. Bewad-J. Prak. Chem. (2) 63, 197 (1901); M. R. Tiollais-Bull. Soc. Ch. Fr. 960 (1947); A. Fleury-Larsoman Bull. Soc. Ch. Fr. 6, 1576 (1939) etc.

The drawing gives the LR. spectrum of one of 3,4-dichloro-N,N-di-sec.-butyl-benzamide.

The following are examples illustrating the invention and marking the examples with initials. Included are halo(alkyl)-N-sec.butyl-N-akyl-benzamides which are new compounds, and a few halobenzamides and a few N,N-dialkylamides not described in literature:

2-fluoro-N,N-di-sec.butyl-benzamide b.p. 106107C at 0.1 mm Hg;

calc. C=71.70 percent, found C=7l.55 percent, calc.H=8.82 percent, found H=8.57 percent PA 272 3-fluoro-N,N-di-sec.butyl-benzamide b.p. 122-124C at 0.6 mm Hg;

calc.C=71.70 percent, found C=71.65 percent, calc.H=8.82 percent, found H=8.75 percent PA 239 4-fluoro-N,N-di-sec.butyl-benzamide calc.C=C=7l.70 percent, found C=7l.55 percent, calc.H=8.82 percent, found H=8.60 percent calc.F=7.56 percent, found F=7.65 percent PA 213 2-chloro-N,N-di-sec.butyl-benzamide b.p. 115-117C at 0.1 mm Hg;

calc.C=67.28 percent, found C=66.99 percent, calc.H=8.28 percent, found H=8.19 percent PA 215 3-chloro-N,N-di-sec.butyl-benzamide b.p. 145146C at 0.5 mm Hg;

calc.C=67.28 percent, found C=66.92 percent, calc.H=8.28 percent, found H=8.l2 percent calc.Cl=13.24 percent, found Cl=l=13.37 percent PA 530 3-chloro-N-n.butyl,N-sec.butyl-benzamide b.p. 121C at 0.05 mm Hg;

calc.C=67.28 percent, found C=67.41 percent, calc.H=8.28 percent, found H=8.36 percent PA 625 3-chloro-N,N-di-sec.amyl-benzamide b.p. 130C at 0.05 mm Hg;

calc.C=69.02 percent, found C=68.83 percent, calc.H=8.86 percent, found H--8.82 percent 4-chloro-N,N-di-sec.butyl-benzamide b.p. 123-124C at 0.2 mm Hg;

ca1c.C=67.28 percent, found C=67.00 percent, ca1c.H=8.28 percent, found H=8.04 percent 2-bromo-N,N-di-sec.butyl-benzamide b.p. C at 0.05 mm Hg;

calc.C=57.70 percent, found C=5 7.99 percent, calc.H=7.l0 percent, found H=7.23 percent PA 337/3Br 3-bromo-N,N-di-sec.butyl-benzamide b.p. 153-154C at 0.05 mm Hg;

calc.C-=57.7O percent, found C=57.79 calc.H=7.1O percent, found H=7.28 percent PA 525 3-bromo-N,n.butyl-N-sec.butyl-benzamide b.p. 138-139C at 0.05 mm Hg;

calc.C=5 7.70 percent, found C=57.74 calc.H=7.10 percent, found H=7.07 percent PA 523 3-bromo-N,N-di-sec.amyl-benzamide b.p. 126127C at 0.05 mm Hg;

calc.C=60.00 percent, found C=59.74 calc.H=7.70 percent, found H=7.58 percent PA 238 4-bromo-N,N-di-sec.butyl-benzamide b.p. 135-136C at 0.1 mm Hg;

calc.C=57.70 percent, found C=57.51 calc.H=7.l0 percent, found H=7.13 percent PA 494 2-iodo-N,N-di-sec.butyl-benzamide b.p. 147148C at 0.1 mm Hg;

calc.@50.l5 percent, found C=50.41 calc.H=6.l7 percent, found H=6.33 percent PA-491 3-iodo-N,N-di-sec.butyl-benzamide b.p. 141C at 0.05 mm Hg;

calc.C=50.15 percent, found C=49.92 calc.H=6.17 percent, found H=5.96 percent PA 287 4-iodo-N,N-di-sec.butyl-benzamide b.p. 147C at 0.05 mm Hg;

calc.C--50.15 percent, found C=50.19 calc.H=6.17 percent, found H=6.17 percent PA 336 2,3-dichloro-N,N-di-sec.butyl-benzamide m.p. 68-69C crystals from hexane;

calc.C=59.61 percent, found C=59.54 ca1c.H=7.00 percent, found H=6.85 percent PA 214 2,4-dichloro-N,N-di-sec.butyl-benzamide m.p. 7375C crystals from ligroin;

calc.C=59.6l percent, found C=59.67 calc.H=7.00 percent, found H=7.03 percent PA 412 I 2,5-dichloro-N,N-di-sec.butyl-benzamide m.p. 99l00C crystals from ethanol/H O;

calc.C=59.6l percent, found C=59.56 percent, ca1c.H=7.00 percent, found H=6.79 percent PA 227 2,6-dichloro-N,N-di-sec.butyl-benzamide m.p. 77-79C from ligroin;

calc.C=59.61 percent, found C=59.73 percent, calc.H=7.00 percent, found H=7.00 percent PA 106 3,4-dichloro-N,N-di-sec.butyl-benzamide crystals: b.p. (in the state of overmelting) 144-145C at 0.1 mm Hg;

calc.C=59.6l percent, found C=59.49 percent,

percent,

percent,

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percent,

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percent,

percent,

percent,

percent,

. calc.H=7.00 percent, found H=6.82 percent calc.Cl=23.46 percent, found Cl=23.35 percent, n 1,531 (IR. spectrum in drawing) 3,4-dichloro-N-n.propyl,N-sec.butyl-benzamide b.p. 130-131C at 0.05 mm Hg; calc.C=58.34 percent, found C=5 8.34 percent, calc.H=6.65 percent, found H=6.74 percent PA 5 71 3,4-dich1oro-N-isopropyLN-sec.butyl-beenzamide b.p. 116C at 0.05 mm Hg; calc.C=5 8.34 percent, found C=58.60 percent, calc.H=6.64 percent, found H=6.70 percent PA 631 3,4-dichloro-N-ethyl,N-sec.butyl-benzamide b.p. 127l28C at 0.05 mm Hg; calc. @5694 percent; found C=57.06 percent, calc;H=6.25- percent, found H=6.19 percent PA 514 3,4-dichloro-N-n.butyl,N-sec.butyl-benzamide b.p. 139140C at 0.02 mm Hg; calc.C=59.61 percent, found C=59.46 percent, calc.H=7.00 percent, found H=6.86 percent PA 566 3,4-dichloro-N-isobutyl,N-sec.butyl-benzamide b.p. 133-134C at 0.05 mm Hg; calc.C=59.61 percent, found C=59.5 3 percent, calc.H=7.00 percent, found H=6.66 percent PA 623 I 3,4-dichloro-N,N-di-sec.amyl-benzamide b.p. 154C at 0.05 mm Hg; calc.c=61.82 percent, found C=6l.82 percent, calc.H=7,63 percent, found H=7.59 percent PA 634 3,4-dichloro-N-sec.amyl,N-sec.butyl-benzamide b.p. l41142C at 0.1 mm Hg; calc.C=60.76 percent, found C=60.49 percent, calc.H=7.33 percent, found H=7.19 percent PA 234 3,5-dichloro-N,N-di-sec.butyl-benzamide mp. 122l23C, crystals from ethanol; calc.C= 59.61 percent, found C=59.86 percent, calc.H=7.00 percent, found H=7.03 percent PA 538 3,5-dichloro-N,n.butyl,N-sec.butyl-benzamide m.p. 5759C, crystals from ligroin; calc.C=59.61 percent, found C=59.63 percent, calc.H=7.00 percent, found H=6.98 percent PA 537 3,5-dichloro-N,N-di-sec.amyl-benzamide m.p. 7 l-73C, crystals from hexane; calc.C==6l.82 percent, found C==62.07 percent, calc.H=7.63 percent, found H=7.63 percent PA 484 3,4-dibromo-N,N-di-sec.butyl-benzamide b.p. 16016lC at 0.05 mm Hg; calc.C=46.06 percent, found C=46.35 percent, calc.H=5.41 percent, found H=5.29 percent PA 606 3,5-dibromo-N,N-di-sec.butyl-bezamide m.p. 1 18120C, crystals from petroleum ether; calc.C=46.06 percent, found C=46.12 percent, calc.H=5 .41 percent, found H=5.24 percent PA 569 3,5-diiodo-N,N-di-sec.butyl-benzamide m.p. l19-121C, crystals from ethanol/H O; calc.C=37.l4 percent, found C=37.16 percent, calc.H=4.36 percent, found H=4.37 percent calc.l=52.32 percent, found l=52.07 percent PA 504 2-bromo,5-chloro-N,N-di-sec;butyl-benzamide m.p. 104-'-l05C, crystals from ligroin;

calc.C=51.97 percent, found C=51.88 percent, calc.H=6.l0 percent, found H=6.0l percent PA 489 3-bromo,4-chloro-N,N-di-sec.butyl-benzamide b.p. 154-155C at 0,1 mm Hg;

calc.C% 1.97 percent, found C=52.10 percent, calc.H=6.l0 percent, found H=6.39 percent PA 626 3-bromo,5-chloro-N,N-di-sec.butyl-benzamide m.p. ll8-120C, crystals from methanol/H O;

calc.C=51.97 percent, found C=52.00 percent, calc.H=6. 10 percent, found H=6.08 percent PA 518 3-bromo,4-fluoro-N,N-di-sec.butyl-benzamide b.p. 129C at 0.05 mm Hg;

calc.C=54.55 percent, found C=54.55 percent, calc.H=6.41 percent, found H=6.31 percent PA 614 4-chloro,3-iodo-N,N-di-sec.butyl-benzamide b.p. 157C at 0.1 mm Hg;

calc.C-45.76 percent, found G=45.66 percent, calc.H=5.38 percent, found H=5.57 percent PA 619 3-iodo,4-bromo-N,N-di-sec.butyl-benzamide m.p. 8486C, crystals from petroleum ether;

calc.C=41.l2 percent, found C=41.13 percent, calc.H=4.83 percent, found H=4.83 percent PA 300 2,3,5-trichloro-N,N-di-sec.butyl-benzamide m.p. =11 l-112C, crystals from ethanol;

ca1c.C=53.51 percent, found C=53.52 percent, calc.H=5.99 percent, found H=5.88 percent calc. Cl=31.59 percent, found C1=31.56 percent PA 488 2,3,4-trichloro-N,N-di-sec.butyl-benzamide ca.lc.C=53.5l percent, found C=53.79 percent, calc.H=5.99 percent, found H=6.12 percent PA 633 2,4,6-trichloro-N,N-di-sec.butyl-benzamide m.p. 69-71C, crystals from methanol/H O;

ca1c.C=53.5l percent, found C=53.83 percent, calc.H=5.99 percent, found H=5.98 percent PA 621 3,4,5-trichloro-N,N-di-sec.butyl-benzamide calc.C=53.5l percent, found C=53.22 percent, calc.H=5.99 percent, found H=5.85 percent PA 307 2,3,6-trichloro-N,N-di-sec.butyl-benzamide b.p. 171C at 0.05 mm Hg;

calc.C=5 3.51 percent, found C=53.27 percent, calc.H=5.99 percent, found H=5 .96 percent PA 338- 2,4,5-trichloro-N,N-di-sec.buty1-benzamide b.p. 107C, crystals from petroleum ether/- hexane;

calc.C=53.51 percent, found C=53.3l percent, calc.H=5.99 percent, found H=5.92 percent calc. C1=3l.59 percent; found C1=31.03 percent PA 510 2,3,5-tribromo-N,Ndi-sec.butyl-benzamide m.p. 116-1l7C, crystals from petroleum ether;

calc. C=38.33 percent, found C=38.70 percent, calc.H=4.29 percent, found H=4.32 percent 2,3,5-triiodo-N,N-di-sec.butyl-benzamide m.p. ll41l6C, crystals from hexane;

calc.C=29.48 percent, found C=29.59 percent, calc.H=3.30 percent, found H=3.13 percent calc.l=62.30 percent, found 1 62.34 percent PA 645 m.p. 124l26C, crystals from petroleum ether;

calc.C=42.09 percent, found C=42,25 percent; calc.H=4.7l percent, found H=4.65 percent PA 445 3-chloro,4-methyl-N,N-di-sec.butyl-benzamide calc.C=68.l9 percent, found C=67.93 percent, calc.H=8.55 percent, found H=8.83 percent PA 226 3-methyl-N,N-di-sec.butyl-benzamide b.p. 111C at 0.1 mm Hg;

calc.C=77.68 percent, found C=77.59 percent, calc.H=10.l9 percent, found H=10.17 percent PA 233 3,4-dimethyl-N,N-di-sec.butyl-benzamide calc.C=78.l 1 percent, found C=77.95 percent, calc.H=l0.4l percent, found H=10.4l percent PA 481 3-methyl,4-bromo-N,N-di-sec.butyl-benzamide b.p. 154C at 0.05 mm Hg;

calc.C=58.90 percent, found C=5 8.72 percent, calc.H=7.4l percent, found H=7.6l percent PA 232 3-fluoro,4-methyl-N,N-di-sec.butyl-benzamide calc.C=72.42 percent, found C=72.l8 percent, calc.H=9.l2 percent, found H=9.21 percent PA 480 3,5-dimethyl-N,N-di-sec.butyl-benzamide m.p. 525C, crystals from ethanol/H O;

calc.C=78.l 1 percent, found C=78.23 percent, calc.H=l0.4l percent, found H=10.33 percent PA 237 2-methyl-N,N-di-sec.butyl-benzamide calc.C=77.68 percent, found C=77.44 percent, calc,H=l0.l9 percent, found H%.94 percent PA 216 4-methyl-N,N-di-sec.butyl-benzarnide calc.C=77.68 percent, found C=77.78 percent, calc.H=lO.l9 percent, found H=l0.08 percent Furthermore, we have also surprisingly found that as herbicides may also be used halo(alkyl)N-sec.butyl-N- alkyl-benzamides comprised in the general formula (I) and obtained according to conventional methods from single halo(alkyl)benzoic acids, optionally in admixture with each other, as well as halo(alkyl)N-sec.butyl- N-alkyl-benzamide mixtures, according to the invention, and obtained by amidating mixtures of halo(alkyl)benzoic acids occurring from one single halogenation operation of the benzenic nucleus carried out according to conventional methods. Synergistic effects were observed in the behavior of these mixtures.

Hereunder, in a non-limiting way, are listed the preferred compounds of the invention:

3-chloro-N,N-di-sec.butyl-benzamide; 3-bromo-N,N-di-sec. butyl-benzamide; 3,5-dichloro- 8 N,N-di-sec.butyl-benzamide; 3-bromo, 4-chloro-N,N- di-sec.butyl-benzamide; 3,4-dichloro-N,N-di-sec.butylbenzamide; 3,4-dichloro-N-sec.butyl-N-n-butylbenzamide; 2,4-dichloro-N,N-di-sec.butyl-benzamide; 2,6-dichloro-N,N-di-sec.butyl-benzamide; N,N-disec.butyl-amides from a mixture of mono-chlorobenzoic acids (about m. chloro 83 percent; o.chloro 15 percent; p.chloro 2 percent); N,N-disec.butylamides from a mixture of trichlorobenzoic acids (about 2,3,6-trichloro percent, 2,3,5- trichloro 25 percent); 3-iodo-N,N-di-sec.butylbenzamide; 3-methyl-N,N-di-sec.butyl-benzamide; and 2,3,5-trichloro-N,N-di-sec.butyl-benzamide.

The compounds of this invention are active both in preemergence as well as in post-emergence. The specific characteristic, however, that distinguishes their herbicidal action is the very marked selective action in pre-emergence. In fact, while these compounds exert a considerable and determining phytotoxic action on infesting species, particularly on gramineae, in quantities useful for the herbicidal effect, they leave unharmed important agrarian plants such as for instance: rice, wheat, corn, peas, etc.

The effects on the vegetation manifest themselves substantially through the permanent stopping of the growth of the small plants in their earliest stages of development. The green color of the leaves is intensified, but the growth is completely inhibited and after a certain time the small plants die.

On the other hand, known products of a similar structure impart in the small plants symptoms of suffering from chlorosis and substantially differ from the compounds of this invention in their herbicidal activity either because of a smaller intensity or for lack of selectivity or for a remarkably lower selectivity, particularly with respect to gramineae.

TABLE 1 following gives recorded demonstrative data of the activity of a number of compounds according to the invention compared to data of known compounds having similar structure, thus exemplifying the subject matter of this application. It is understood that all the data given herein shall have no limiting character on the object of this invention.

These data have been obtained from a treatment carried out by uniformly spreading, by sprinkling, on the soil a quantity of active substance in a hydroacetonic solution corresponding to 6 kg/ha, 1 day after sowing. This quantity was reduced in the case of some more active products, down to 2 kg.

The data reported refer to the action on the useful plants limited to the products that are more active on the infestants.

The infesting species and the agrarian species have been indicated in Table l by letters, as follows: Infesting species:

A Amaranthus retroflexus L.

B Artemisia vulgaris L.

C Chenopodium album L.

D Echinocloa crus-galli R.S.

E Setaria glauca L.

F Vicia sativa L.

Agrarian species:

G Avena sativa (oats) H Beta vulgaris L. (sugar-beet) I Phaseolus vulgaris (bean) L Pisum sativum L. (pea) M Solarium Lycopersicum L.

N Triticum vulgare L. (wheat) 3 considerable activity with damages that definitely O Zea mais L. (corn) impair the further development of most of the small P Ory za sqtivg L. (ricel 7 V 7 plants; an activity degree already useful for practical Method of evaluation of the results (of tests): purpfses;

0 no activity and no difference with respect to the 5 4 maxlinum of actwlty wlth lack germmauon. or control, total containment of the small plants in the emerging 4. v t V i t g 1 slight differences with respect to the control; In the case of an intermediate activity between two 2 activity of a certain degree with partial damages classes of the scale, both values are recorded with the that do not, however, in general, jeopardize the vitality to one which corresponds to the preeminent activity preof the small plants; ceding.

TABLE 1 z-l g-l Mark Product ha. A B C D E F ha. G H I L M N O P PA215. 3,ch1oro-N,Ndlsec. butyLbenzamide 6 1-2 1-2 1-2 3 3 1-2 6 0 0 0 PA321. 3,chloro-N,N-diethyl-benzamldm 6 1-2 2 1-2 1 1 1 6 1 1-0 2 2-3 0-1 2 PA322. 3,chlor0-N,N-dl-n.propyl-benzamide 6 1 1-2 0-1 1 0-1 1-0 PA213. 2,chloro-N,N-disec.butyl-benzamide 6 2 1 0-1 2-3 3 0 6 0 0 0 0 0 2,chloro-benza.mide 6 2 1 2 0-1 0 2-3 6 0-1 0-1 PA337/3/Br 3,bromo-N,N-disec.butyl-benzamide 6 4-3 3 4 4 4 1-0 6 0 1 1 0 1-2 0 0 O PA396 3-bromo-N,N-di-n.butylbenzamide 6 1 1-2 0-1 0-1 0 0 PA499 3-brom0-N,N-di-aLlyI-benzamide 6 4-3 3 3 3 3 3 PA521 3-bromo-N,N-di-isobutyl-benzamide 6 1 1 1 1-2 1-2 0 PA214 2,4-dichloro-N,N-dlsec.butyl-benzsmide 6 3-4 3-2 3-2 4 4 0 4 2-3 2 1-2 3-4 3-4 0 2 1 1 1 3-2 3 0 PA283 2,4-dlchloro-N,N-dlethyl-benzamide 6 1 2 1-2 1 1 PA280 2,4-d10hloro-N,N-dl-n.propyl-benzamlde- 6 3 2-3 2-3 2 1 PA281.-- 2,4-dlchlor0-N,N-di-isopropyl-benzamlde 6 1-2 2 0-1 0-1 0-1 PA282 2,4-dlchloro-N,N-di-n.butyl-benzamlde 6 2 0 2 1 1 PA106 3,4-dichloro-N,N-di-sec. butyl-benzamlde. 6 3 3 3 4 4 4 2 1-2 1-2 3-4 3-4 2 1 0-1 0-1 2 3-2 PA61 3,4-djchloro-N,Ndiethy1-benza.mide 6 3-4 3-4 a a 4-3 2 3 3 1 2 PA105 3,4-dichloro-N,Ndi-'n.butyl-benzamide 6 1-2 1-2 1 2 3 1-0 0-1 0-1 0-1 1 PA259 3,4-dichloro-N,N-di-iso-butyl-benzamide 6 1-2 2 1-2 3-2 3-2 PA514 3,4-(11chloro-N-n.butyl-N-sec.butyI-benzamide 6; 1 0-1 2 2 35 4-2 2 IIIIIIIIIIIII 1 2 PA631 3,4-dlchloro-N-ethyl,N-sec. butyl-benzamide. 6 2 2 3 3 3 PA325- 3,4-dlcl loro-N-ethyLN-n.butyjjgenzamlden 6 3 v 2 2 O-1 PA234 3,5-dich1oro-N,N-dl-sec.butyl-benzamlda 6 2-3 1-2 2 4 4 4 2 1 2-1 4 4 2 1-2 0-1 1 4 4 1 2-3 3-4 0-5 2-1-3-2 PA291 3, S-dichloro-N, N-diethyl-benzamide 6 3-4 4 3 4 4 4 3 3-4 3 2-3 3 2 2-3 3 2-3 1-2 2-3 PA292 3,5-dichloro-N,N-din. butyl-benzamide 6 4-3 3-4 3 4 4 4 3-4 3-4 3 4-3 4 2 3 2-3 2 3 4-3 PA294 3, 5-dichloro-N, N-di-n. butyl-benzamide- 6 O-1 0-1 1 2 3 IA226 3,methy1- ,N-di-sec. butyl-benzamlde 6 2 1-2 1-2 4 4 4 1-2 1-2 1 3 3-4 2 1-0 1 0-1 2-3 2 PA383 3,methyl-N,N-diethyl-benzamide- 6 2 3 2 0-1 0-1 2 P113234 3, methyl-N,N-din. propyl-benzami 6 1 2 2 1-2 0-1 1-2 PA386 3,methyI-N,N-di-mbutyl-benzamidm- 6 3 1-2 2-3 0-1 0-1 0-1 PA385 3,methyl-N,N-di-isoprppyl-benzyde 61-2 2 1 1-6 0-1 0-1 PA300 2,3,5-trich1oro-N,N-di-sec.butyl-benzamrde 6 1 1 1-2 4 1 1 l-2 2 1 1-0 1 1 0-1 0-1 PA303 2,3,fi-trlchloro-N,N-d1-n.propy1-benzam1de 6 3 1 2-1 4 2-3 1 1-2 2 2-1 1 1 1v 1 1 1 PA302 2,3,5-trlchloro-N,N-di-iso-propyl-benzamlde 6 2-3 2 3 8 2 2 3 1 2-1 1-2 2 PA439- 3,0hloro-benzolo acid- 6 0 0 0 PA577 3,bromo-benzolc acid.. 6 0 0 0 PA44l 6 0 0 0 Acid.... 6 O 0 0 PA440 6 0 0 0 1311304" 6 1 1 0 PA442 6 1 0 0 a W n L 12 Also the effects deriving from the phytotoxic action of the compounds put to comparison, as already stated,

pletely dify modest exnce in behavthat '7 '11'51 alkyljN fi -dialkylbenzamides with an alkyl having four carbon atoms, different than sec.butyl, are almost inactive or very much less active compared to the halo(alkyl)N,N-di- N,sec.butylpurposes the jectof m teStS' mo H'IL MNO P "Hbw' structural variation'of a relativel lt is also noted 7W -benzamides and the halo(alkyl) ,alkyl-benzamides, so that for practicel first-mentioned compounds cannot be used,

TABLE 2 reports the activity data of other comds that fall within the class which is the ob carried out with the same technique used for the tests A B o D E F manifest themselves on the plants in a com ferent way.

tent can lead to such a substantial differe ior and effects, is still not clear.

sec.butyl poun this invention. This data has been obtained fro n n n n u m u u I -00 .00 l 10 u n 0 000 n n -10 n n u 000 n h n 663 n n u u 2100 u u 1 m. "n H 43H444MH 44H H4444HH 3433 3 H33H44H2 44 3 3344 431 or A 2% 2 2 3111332 321 23211 1% m l j 2431 3011310 H21.. 2 211 m were m a H? 2 21 m 21l2H10 m 229.2 2 3%22 u but. u m 1.. n 1 1.. m h 6642 666664 21 666 6664215 0 3 ,83 ,1 89 1 1 From the data recorded on Table 1, it will be seen that in general the herbicidal activity of the halo(alkyl- )N,N-dialkylbenzamides which do not fall within the field of this invention is considerably less intense than that of the compounds according to the invention. It 5 ,N-dialkyl- ,5-dichloro-N,N- 5-dichloro-N,N-di-n.propyl- 2,3,5-trichloro-N,N-diisoprised by the have a very diffused ry active, in particbut also exert, however, a phytotoxic action of considerable intensity on useful plants and in particular on useful gramineae. l 5 W useful gramineae in operational ouantities for full effectiveness against the infesting of Table 1.

TABLE 2 On the contrary, the phytotoxic action of the prodthis ingqijgti on, although acting inting gramineae, has no effect on the ark Product N-di-sec. butylbenzamide.

n u n. u u n n u n n u n u u u u n n n u u n u n e m on m n n n n m mu n n u u n n n .me mm u m e e a a e a mm .3 m m w m a a m mmmm mm m m m a m m m .d m m h. mm 21% e m 1 m m m z z 1 me m mmm, m m .d w. e e z m m m w iwwt a mm b b m Z u a w b n .b u w u the. 1. 1. m b w. w. b w. w 1% mum w WW a L. W. W. m m w m m y m m H mm mm mm m m m b W. 4 b b m b b b w f m lN m m. m m m a b V, a c m m mnemw s N m N a a a N N m a magm a C r .1 l i 1 c M. a a m a a a N mwtwm m m m N, N, N. m w mN NN N N 0 N N 0 0 OMW hI .m N N N. 1 N. N. m mmhr rrn w m 1N. 0 0 0 N 0 0 0 mnm wb .mb mmw b h N 1 N. 4 M M n m m. m w 4 c y N 000 h h an o o m m 0 m m m 0 m mmm .m .c l r r r n M0 m m c h c "D m moomt. w m .c. t t 1d m m w .m m m m m m fl ,m m s 5 mm b b 2 H a e L. b Ii n 4, 3 3 3 3 3 2 2 2 2 3 2 33332 233 333 2 n n u n u n n n u n n n u n u n n H m n H n n U n h u n n n n u u n u s n u n n n n n I 51 7 9 6 4. 2 7 894 31 6 8 AA A A A 7 PP P P P P P P P P P PPP PPP WPPP P P will also be noted that some of the halo-N benzamides, such as for instance: 3 diethylbenzamide,

benzamide,

propylbenzamide (compounds not com general formula of this invention) herbicidal action and besides are ve ular against infesting gramineae,

ucts according to tensely on the infes yl-benzamide.

TABLE 2-Continued Kg./ Mark Product ha.

I'AISl-t 3,4-(1!chloro-N seebutyl,N,n.butyl-benzamlde g 2 I'Msn 3,bromo,4-chloro,N,N-di-sec.buty1-benzamide 2 2 PA445 3,chlor0,4methyl,N,N-di-sec.butyl-benzamido g 2 H226 t ykNrlitd r wWW W W----- 2 Wgfl 2 PA233 3,4-dlmethy1-N,N-d1-sec.buty1-benza.mide 2 1 2 a o 6 PA481 3,methyl-4,bromo-N,N-di-sec.butyl-benzamide 6 6 0 0 0 1 0 (l a0 0 00 000.... PAK 2-..... Mixture oftrichloro-N,N-di-sec.butyl-benzamides 6 4-3 4 3-4 4 4 0 6 1 23 3-4 3 3 0 0 0 (2,3,6 c13=75%;2,s,5 o13=25%). 4 s 3 a 4 4 0 a 0 2 a 2 1 o 0 2 2-3 1-2 2 4-3 4-3 0 PAKI Mixture ofmonochloro-N,N-diseebutyl-benzamides 6 3 3-4 2-3 3-4 4 0-1 6 0 0 0 0 0 0 0 (a C1=s3.1%;201=14.1%;401=2%). 4 2 2 2 a a 0 a 0 o 0 0 o 0 2 0-1 o (H 1-2 1-2 0 PAK3 Mixture of dichloro-N,N-di-sec.butyl-benzamides 6 3 2 3 4 4 (2,5 C1z=70%; 2,3-Clz=23%; a,4-012=7%). 4 3-2 2 3-2 4 4 2 2 1 1-2 a a PAK4 Mixture oftrichloro-N,N-di-sec.buty1-benzamides 6 3-2 1-2 2 4-3 4 (2,4,5-Cla=66%;2,3,4-C13=33%). 4 2 1 1-2 4-3 4 2 1 11-1 0-1 3 3-4 The following illustrates in more detail the range of TABLE 3 reports data on the herbicidal activity the activity of PA 106, though, of course, the reported 30 against infesting herbs, while TABLE 4 reports data data are to be taken purely as a demonstrative example concerning the activity on useful species of agricultural of the herbicidal activity of this product. It therefore cultivations. These tables employ the criterion exmust be considered as nonlimitative of the invention plained previously. The product was spread on the soil whose scope includes the use of this herbicide also one day after sowing, in quantities of 1, 3, 6, 8, l0, 12 against other weeds and other agricultural cultivations 35 and 14 leg/ha.

not listed herein, as well as particular procedures of treatment required by accidental needs of the disherbr- In the case of gladiolus, the treatment was carried out TABLE 3 Doses in ka/ha infesting species l 3 l0 12 14 Panichum Dichotomi florum M. 2 3/4 4 4 4 4 4 Digitaria sanguinalis L. 2/3 4/3 4 4 4 4 4 Sorghum sp. 1 3 4 4 4 4 4 Echinochloa crus-galli R;S. 0/ l 3 4 4 4 4 4 Seraria glauca L. 2/3 3 4 4 4 4 4 Papaver rhoeas L. O l 2 3 4 4 4 Amaranthus retroflexus L. 0 U2 3 4/3 4 4 4 Chenopodium album L. O l 3 2/3 3 3 3/4 Artemisia vulgaris L. O l 3 3 3 4/3 4 Portulaca aleracea L. 0 H2 3 3/4 4 4 4 TABLE 4 Doses in ksr/ha Agrarian species 1 3 6 8 10 l2 l4 Phareolus vulgaris L. (beans) 0 0 O 0 0 0/1 0/1 Pisum Sativum L. (peas) 0 0 0 0 0 0 0 Brasgica oleracea L. (cabbage) 0 0 0/ l 1 U2 U2 2 Soja Hispr'fla LT (sofa) M 0 0 0 0 0/1 OH OH Hordeum vulgare L. (barley) 0 0 0 0 OH OH 0/ I Zea mais L. (maize) 0 0 0 0 0 0/1 I Berg vulgaris L. (sugar beet) 0 0 l 1 H2 2 2/3 674mm?" 0 0 0 0 0 0 0 T r iticu rr vulgare (wheat) 0 0 0 OH OH 1 l Brassica 70312 L. (Colza) 0 0 l l/2 2/3 3 3 Oryza saliva L. (rice) 0 0 0 O 0 O OH Avena saliva L. (oats) 0 O 0 0 OH OH 1 The compounds according to this invention are either liquids or crystalline solids, generally slightly soluble or practically insoluble in water and soluble in common organic solvents. As is known, because of the necessity of distributing small quantities of active principles over large surface areas, the herbicides are not used as such in the disherbing treatment but are used as compositions that containthem together with solid inert substances that act as carriers and as diluents or together with other substances that will facilitate their dispersion in diluting medium such as water, before use.

Dependingon the surrounding conditions and on the technical means available, preference may be given to one type of composition rather than to another.

Either solid or liquid compositionscan be used. Solid compositions in the form of granules are prepared either by thoroughly mixing together the active substance with solid inert carriers such'as: bentonite, calcium carbonate, vermiculite, attapulgite, pyrofillite, sepiolite, phosphorite, superphosphates, etc., or by spraying the active substance, dissolved in a volatile solvent, onto the granular carrier, mixing the whole and then drying the granules.

The contents in active substance may vary within wide limits, for instance between 0.25 and 80 percent, but preferably between 0.5 and percent. The particle size of the granular carrier may vary from 0.1 mm' to 4 mm, but preferably from 0.15 to 0.7 mm.

The granular compositions are among the preferred compositions because'their distribution on the soil can be carried out by use of equipment normally available on agricultural farms. Powdery compositions may be prepared by recourse to the abovementioned technique, using as a carrier calcium phosphate, calcium carbonate, kaolin, bentonite, Fullers earth, talc, pyrofillite, calcium silicate, superphosphate, etc., by grinding the coarse powders until attaining the desired fineness.

The so-called wettable powders are obtained by incorporating one or more surfactant agents into the powders. By dispersing these wettable powders in water, it is possible to obtain aqueous suspensions at the desired concentrations in active substance. These aqueous dispersions are sprayed onto the soil.

Liquid emulsifiable compositions are prepared by dissolving the active substance in an inert solvent, preferably slightly soluble in water, such as for instance benzene, toluene, and by adding a surfactant agent.

When these compositions are added to water, emulsions are obtained in which the solvent phase is dispersed in the aqueous phase while the active substance is maintained dissolved in the dispersed phase. In this way a uniform distribution is obtained of the active substance in the aqueous composition which is sprayed onto the soil.

In the preparation of wettable powders and of emulsifiable concentrates, emulsifying-dispersing agents of the anionic, nonionic or cationic type may be used. Among the agents of the anionic type may be listed: sodium dodecyl-benzene-sulphonate, calcium naphthalene-sulphonate, laurylsulphate; of the active cationic type quaternary ammonium compounds may be used, such as: cetylpyridinium-bromide, dodecylbenzylmethylammonium chloride, -di-(hydroxyethyl)-benzyldodecylammonium chloride; among the nonionic agents are condensation products of ethylgn oxidg with aliphatic alcohols, amines, fatty acids, alkylphenols. All of the above compounds are readily commercially available.

The preparation of compositions of any type containing compounds of this invention presents no difficulties as they can be prepared easily by making use of the known techniques. If desired, herbicides with a complementary algacidal activity or pesticides, fertilizers,

etc. may be incorporated into these compositions. The use of any type of composition, independently from the techniques followed in the disherbing, falls within the scope of this invention.

Among the preferred types of composition we cite hereinbelow for illustrative but not limiting purposes just a few:

Granulate: PA 106 5 percent, 1 percent sodium 'di-iso-octylsulphosuccinate, 94 percent bentonite in granules with a 4 (diameter) for percent between 1 and 0.5 mm. It is prepared by suitably dissolving 5 parts of PA 106 1 part of sodium di-iso-octylsulphosuccinate in 1 part methylene chloride, and by then spraying the solution onto the granular carrier until attaining complete absorption. The solvent is then removed by evaporation and is then recovered.

Granulate: PA 106 5 percent, sepiolite 95 percent in granules of a diameter comprised, as an average, between 0.5 and 0.25 mm. The mixture is prepared either by directly mixing or by spraying-onto the granular carrier the active substance dissolved in a solvent.

Emulsifiable oil: PA 106 50 percent, xylene 30 percent, Soprofor NPA 20 percent (oxyethylated and sul- 'phonated fat). It is prepared by directly mixing the components under shaking.

Emulsifiable oil: PA 106 50 percent, xylene 40 percent, Atlox 5 848 6 percent, Atlox 89 l 6? 4 percent (derivatives from polyoxymethylene sorbitanesters of fatty acids and their resinous derivatives in admixture with alkylarylsulphonates). It is prepared by directly mixing the components under shaking.

The quantities that are used in the disherbing vary considerably in relation to the contents in active princi- 7 ple, to the species of the plants, and to the treatment technique. In average these quantities must be such as to supply from 1 10 kg of active principles per hectar of soil. We have, for instance, used with much success granular compositions containing 5 percent of compound or compounds according to the invention in the disherbing of rice from Echinocloa crus-galli and from Panicum dichotoniflorum, infesting gramineae predominant in rice fields, in such quantities as to supply to the soil 2 10 kg of active principles. In this case the pronounced selective action of the products according to this invention with regard to these infesting plants is exploited.

It is quite known to the man skilled in the art that the disherbing of rice involves particular difficulties both with respect to the close botanical affinity of the weeds with the useful plants, as well as with respect to the particular surrounding conditions of rice growing.

As is known, the disherbing of those infestants may be carried out either in post-emergence or in preemergence. In this latter case the herbicide must exert its action on a submerged or flooded field, since the chambers of the rice fields are flooded immediately after sowing; the herbicide must, therefore, possess particular characteristics besides the selective action, at sitm stbavs a ntaslion was particular environment, it must be non-volatile, it must be very little soluble in water in consideration of the fact that in the areas of the rice fields there is a continuous renewal of water and the out-flowing or downstream water may reach other existing cultivations or it may be used for irrigation or other like purposes. The herbicide must therefore remain uniformly distributed on the soil also under these particular conditions and it must exert its action for long stretches of time.

It is extremely difficult to find combined in the same single product with a herbicidal action all these characteristics.

We have found that compounds comprised by the general formula (I), have the required requisites for being used by the farmers to their full satisfaction in this particular field of application.

The development of the species indicated above is practically inhibited when the small plant is in the sprouting stage. The disherbing may be carried out either before sowing or after the sowing; In any case one obtains the permanent stopping of the vegetative development and the subsequent death of the infesting plants, while the rice remains completely unharmed. This is a further aspect of the invention which is of great technical and economical importance which will be illustrated in the following by some examples of a non-limiting character.

EXAMPLE No. l

A series of pots were prepared filled with rice-field earth. Into these were then sown Echinocloa crus-galli and rice. The earth was then submerged by 10 cm of water and immediately thereafter were uniformly spread on the submerged soil granular compositions,

some of them containing 2 percent of PA 234 and 98.

percent of phosphorite, some others 5 percent of PA 234 and 95 percent of bentonite, in doses graduated from 8 kg of active principle per hectar. The test pots were kept in a conditioned environment at controlled temperature and photo-period.

It was ascertained that under a 3 kg/ha dose of active principle, the growth of the Echinocloa crus-galli was totally inhibited, while the rice, even under the maximum dose, remained undamaged.

EXAMPLE No. 2

Into 2 sq.m. basins containing rice-field soil were sown rice and Echinocloa crus-galli. After having submerged the soil with 10 cm of water, treatments were trol basin the growth of the infesting plant was vigor- 60 ous, equal to 33 plants of Echinocloa crus-galli per sq.m.

EXAMPLE No. 3

In this test a granular composition of PA 106 containing percent of active principle and 95 percent of bentqnits was used 11 s w s t s risd 1. in a e 4 field with areas of from 900 to 1000 sqm on naked soil flooded just shortly before the sowing of the rice. There were used doses of granulate equal to 4, 6, 8 and kg of active substance per hectar of surface. It was ascer- 5 tained that while in the non-treated areas the degree of infestation by Echinocloa crus-galli was considerable, equal to 2500 plants per area, and the development of the rice had been hindered by the competing growing of the infestant, in the areas treated with 6 kg of PA 10 106, the disherbing could for all practical purposes be considered as total. The rice in all the'treated areas had grown vigorously, without suffering any damage even by greater doses of herbicide applied.

In a subsequent plot-test conducted in open field on areas of 80 sq.m planted with rice, when using a granular composition containing 5 percent of PA 106 and 95 percent of bentonite at different growing doses, no phytotoxic effects on the rice could be observed even at a dose of 30 kg/ha of active substance. The following are a few examples of the preparation of compounds according to this invention and of two N-sec.butyl-N-alkylamines not known to the literature.

Preparation of 3-bromo-N,N-di-sec.butyl-benzamide Into a 150 ml flask, provided with a reflux condenser, were introduced 10 g of 3-bromo-benzoyl chloride dissolved in 25 ml of anhydrous C I-I and a solution of 6 g of di-sec.butylamine in 10 ml of anhydrous C l-I and 4.9 g of triethylamine. The whole was then heated to reflux temperature for about 1 hour. The mass was thereupon permitted to cool down to room temperature and the solvent was then removed under a reduced 3 5 pressure. The mixture was then washed with acidulated H O, with H 0 and then extracted with ethyl ether. The etheric extract was dried on anhydrous Na SO filtered and the solvent removed'under reduced pressure. The oily residue was subjected to fractional distillation at 0.05 mm Hg and the fraction passing over at 153l54C was collected. Obtained thereby was 14.7 g of distillate consisting of 3-bromo-N,N-di-sec.butylbenzamide.

The analysis gave:

calculated C 57.70 percent, found C 57.79 percent calculated H 7.10 percent, found H 7.28 percent Preparation of 3,5-dichloro-N,N-di-sec.butyl-benzamide Into a 2,000 ml three-necked flask, cooled externally with ice, were introduced 100 g of dry and well powdered anthranylic acid, suspended in 400 ml of anhydrous benzene. Through a separatory funnel a solution of 100 ml of SO Cl in 200 ml of anhydrous benzene was added to the mass, under vigorous stirring. The addition is carried out in a stretch of time of about 1 hour. The suspension was boiled to reflux temperature for 5 hours, still under stirring. During this operation a strong development of HCl was observed. The mass was then cooled, diluted with an equal volume of ligroin, permitted to stand at 0C for 1 hour and was fi- 65 .nally filtered and washed with ligroin. The precipitate, after drying, was treated with 1500 ml of hydrochloric acid at 8 percent, under constant stirring and heating up to 5 060, C. The whole was then filtered thereby obtaining an insoluble fraction consisting of about 50 g of raw 3,5-dichloroanthranyl acid (melting point 200230C). After crystallization from ethanol/H about 38 g of 3,5-dichloroanthranyl acid with a melting point of from 230 231C were obtained.

g of 3,5-dichloroanthranyl acid were then dissolved, by adding it in small portions at room temperature and under stirring, in 75 ml of concentrated H SO The whole was then cooled down and, keeping the temperature at 0C, added thereto under vigorous stirring, in small doses, was 7.5 g of NaNO On completion of the addition, the stirring was continued for another 2 hours, still maintaining the temperature at 0C. The mass was then poured in a thin flow into ice and was filtered, being careful that the mass did not exceed 0C (one operates always in the presence of ice).

The solution thus obtained was then added in small doses to a double volume of boiling ethanol, keeping the whole under stirring. Once the development of nitrogen had stopped, the whole was cooled down, diluted with H 0 and, after 2 hours at 0C, was filtered by washing with H 0. 7 g of raw product with a melting point of from l84187C were obtained thereby. The product was then crystallized from ethanol/H O.

Into a 150 ml flask, provided with a reflux condenser, were introduced 7 g of 3,5-dichloro-benzoic acid and g of SOCl and the whole was then reflux heated for about 1 hour. Thereupon the excess of SOC1 was removed under reduced pressure in a rotating evaporator. The oil that remained, after purification by fractional distillation, was treated with anhydrous C l-l Added to this was a solution of 4.5 g of disec.butylamine in 10 ccof anhydrous C 11,, and 3.7 g of triethylamine. The whole was then heated to reflux temperature for about 1 hour. Thereupon, the mass was left to cool down to room temperature and the solvent was removed under reduced pressure. The mass remaining was then washed with acidulated H O, with H 0 and finally extracted with ethyl ether. The ether extract was then dried on anhydrous Na SO filtered and the solvent removed under reduced pressure. 9.9 g of white-yellow crystals consisting of 3,5-dichloro- N,N-di-sec.butylbenzamide were obtained.

The mass was then dissolved in a minimum quantity of boiling C H OH and then cooled down to 0C. Thus 8.9 g of white crystals showing a melting point of from l22123C were obtained.

The analysis gave:

calculated C 59.61%, found C 59.86% calculated H 7.00%, found H 7.03%

Preparation of 3 ,4-dic hloro-N-sec.butyl,N-n,butyl-benzamide:

Into a 250 ml flask provided with a reflux condenser, were introduced 24.9 g of 3,4-dichlorobenzoyl chloride dissolved in ml of anhydrous C H a solution of 15.3 g of N-sec.butyl-N,n-butylamine in 20 ml of anhydrous C H and 13.1 g of triethylamine. This mass was heated to reflux temperature for about 1 hour. The whole was then cooled down to room temperature and the solvent was removed under reduced pressure in a rotating evaporator. The mass was then washed with acidulated H O, with H 0 and was extracted with ethyl ether. The ether extract was then dried on anhydrous Na SO.,, filtered and the solvent removed under reduced pressure in a rotating evaporator. The oily residue was subjected to fractional distillation at 0.02 mm Hg and the fraction passing over at 139140C was collected. 30.5 g of distillate constituted by 3,4-dichloro-N-sec.butyl,N,n.butyl-benzamide were obtained. The analysis gave:

calculated C 59.61%, found C 59.44% calculated H 7.00%, found H 6.86%

Preparation of 2,3 ,5 -trichloro-N,N-di-sec.butyl-benzamide:

The acid was prepared according to the known technique, more particularly according to Cohen J. B., Dakin H. D. Soc. 81,1331 (1902).

lnto a 250 ml flask, provided with a reflux condenser, were introduced 10 g of 2,3,5-trichlorobenzoyl chloride in 20 ml of anhydrous C H a solution of 5.3 g of di-sec.butylamine in 7 ml of anhydrous C H and 5 g of triethylamine. This mass was then heated to reflux temperature for about l hour. Thereupon it was left to cool down to room temperature and the solvent was removed under reduced pressure in a rotating evaporator. The mass was then washed with acidulated H O, with H 0 and was then extracted with ethyl ether. The etheric extract was then dried on anhydrous Na SO filtered and the solvent removed under reduced pressure. 12.6 g of yellowing crystals of 2,3,5-trichloro- N,N-di-sec.butylbenzamide were obtained.

The crystalline mass was thereupon dissolved in the minimum quantity of boiling C H OH and cooled down to 0C. Thereby were obtained 11.5 g of white crystals having a melting point of 1 11-112C.

The a is a s calculated C 53.51%, found C 53.52%

calculated H 5.99%, found H 5.88%

calculated C1 31.59%, found C1 31.56%

Preparation of 3-chloro,4-methyl-N,N-di-sec.butyl-benzamide:

Into a 150 ml flask, provided with a reflux condenser, were placed 17.1 g of 3-chloro-4-methyl-benzoic acid (prepared according to French Pat. No. 835,727) and 55.5 g of SOCl and the whole was heated to reflux until complete dissolution. The boiling was continued for another 30 minutes. The excess in SOCl was then removed under vacuum and the residue was subjected to fractional distillation at a pressure of 0.2 mm Hg. The fraction passing over at C was then collected. 17.9 g of the chloride of 3-chloro,4-methylbenzoic acid were obtained.

To these 17.9 g of the chloride of 3-chloro,4-

methylbenzoic acid, dissolved in 60 ml of anhydrous benzene, were added 12.9 g of di-sec.butylamine dissolved in 15 ml of anhydrous C H and 12.3 g of triethylamine. The whole was then boiled to reflux temperature for 1 hour and was then left to cool down to room The two unknown asymmetric amines which are used for preparing the compounds according to the invention, have been synthesized in the following manner.

Preparation of N-sec.butyl,N-sec.amylamine:

Into a 150 ml flask, provided with a reflux condenser, were placed 14.6 g of monosecbutylamine dissolved in 15.5 ml of C H OH. Added thereto was 30 g of 2- bromo-pentane. This mass was then boiled to reflux temperature for -12 hours and thereafter cooled down and neutralized with dilute H SO The whole was then evaporated to dryness. The residue thus obtained was treated with an excess of a percent Mark Product per as on rat LD 50 mg/kg PA 484 3,4-dibromo N,N-di-sec.buty1-benzamide 2.550

PA 489 3,bromo-4,chloro-N,N-di-sec.butyl-benzamide 2.500

PA 631 3,4-dichloro'N,N-di-secbutyl-benzarnide 930 PA 300 2,3,5-trichloro-N,N-di-sec.butyl-benzamide 2.000

PA 234 3,5-dichloro-N,NdLsecbutyl-benzamide 2.000

NaOH solution and extracted with 3 successive portions of ethyl ether. The ether extracts were then together washed with H O, dried on anhydrous Na SO filtered and the ether removed by evaporation. The residue was distilled under atmospheric pressure and the fraction was gathered which passed over at 160-l61C. 15.75 g of N-sec.butyl,N-sec.amylamine were obtained thereby. The picrate shows a melting point of from 6163C (crystals from petroleum ether). The analysis of the picrate gave:

calculated C 48.58%, found C 48.22%

calculated H 6.50%, found H 6.40%

, -dichloro-N,N-di-sec.butyl-benzamidc We claim:

. 3,4-dichloro-N,N-di-sec.butyl-benzamide.

. 3,5-dichloro-N,N-di-sec.butyl-benzamide.

. 2,4-dichloro-N,N-di-sec.butyl-benzamide.

. 2,6-dichloro-N,N-di-sec.butyl-benzamide.

. 3-bromo-N,N-di-sec.butyl-benzamide.

. 3-iodo-N,N-di-sec.butyl-benzamide.

3-bromo-4-chloro-N,N-di-sec.butyl-benzamide. 3,4-dichloro-N,n,butyl-N-sec.butyl-benzamide. 9. 2,3,5-trichloro-N,N-di-sec.butyl-benzamide. l0. 2,3,4-trichloro-N,N-di-sec.butyl-benzamide. U 

2. 3,5-dichloro-N,N-di-sec.butyl-benzamide.
 3. 2,4-dichloro-N,N-di-sec.butyl-benzamide.
 4. 2,6-dichloro-N,N-di-sec.butyl-benzamide.
 5. 3-bromo-N,N-di-sec.butyl-benzamide.
 6. 3-iodo-N,N-di-sec.butyl-benzamide.
 7. 3-bromo-4-chloro-N,N-di-sec.butyl-benzamide.
 8. 3,4-dichloro-N,n.butyl-N-sec.butyl-benzamide.
 9. 2,3,5-trichloro-N,N-di-sec.butyl-benzamide.
 10. 2,3,4-trichloro-N,N-di-sec.butyl-benzamide. 